Water-insoluble metalliferous azo-dyestuffs and process for preparing them



United States Patent 3,084,151 WATER-INSOLUBLE METALLIFEROUS AZO-DYE-STUFFS AND PROCESS FORPREPARING THEM- Richard' Gross, Frankfurt am Main,midi-lasso H'ertel,

WernerKirsbReinhard.Mohr, and WaltenSt'aab, (Etienbach (Main), Germany,assign'ors to-Farbwerlw H'oechst Aktiengesellschaft vormals Meister-Lucius 81 Briining, Frankfurt am. Main, Germany, a corporationofiGermany I No Drawing.v FiledSept. 7, 1960,.Ser. No. 54,360 filaiinspriority, application Germany Sept. '9, 1959 6 Claims. (or. zen-146 Thepresent invention relates to new water-insoluble metalliferousazo-dyestuffs and to a process for preparing them; more particularly itrelates to water-insoluble complex metal compounds of .azo-dyestuffscorresponding to the following general formula.

wherein A and B represent radicals of the benzene or naphthalene series,R represents the radical of a coupling component coupling in a positionvicinal to a -hydroxyl group, especially .a radical. of an arylideof'anaromatic or heterocyclic ortho-hydroxycarboxylic acidoranacylacetic acid and it stands for theinteger 1 or 2.

We have found that new water-insoluble metalliferous azo-dyestufis areobtained by coupling in substance, on the fiber or on another substratumthe diazonium compounds of amines corresponding to the general formulaAW N- B wherein A and B represent radicals of the benzene or naphthaleneseries, with coupling components coupling in a position vicinal to ahydroxyl group, especially with arylides of aromatic or heterocyclicortho-hydroxycarboxylic acids or of acy-lacetic acids,, the dyestuffcomponents being free from groups imparting solubility in water such,for example, as sulfonic acid or carboxylic acid groups, and treatingthe dyestuitsso'obtained with agents yielding metal.

The treatment of the Water-insoluble azo-dyestufis obtainable accordingto the'process of this invention with the agents yieldingmetal maybecarried out by known methods during or after the coupling in substanceor on the fiber. When the dyestufis -are:produc ed ou -the fiber, themetallization may be. effected by addingthe agents yielding metal to thedeveloping bath or by adding:these compounds, to the impregnation bath.The treatment of the dyestuffs with agents yielding metal after thecoupling may be carried out in a second bath which is neutral, weakly.alkaline or weakly acid and contains,.if desired, dispersing agentsanddeter-gents, such as, for example, fatty alcohol polyglycol ether,alkylphenol. polyglycol ether, alkylna-phthol polyglycol ether, fatty.acid poly.- glycol ester or fatty acid. amide polyglycol:e.ther.

As agents yielding metal, there are preferably-usedlfor the process ofthe present invention-compounds yielding copper, cobalt or nickel whichmay be used in the form of their inorganic or organic-:saltssuch, forexample, as

chlorides, bromides, sulfates, nitrates, formates or ace or alkalipolyphosphates.

"ice

suc'h as citric acid or. tartaric acid, or with alkalimeta'l phosphates,such, for example, as alkali. pyrophosphates When :there is used anagent yielding cobalt, the addition of compounds of hexavalent chromiumor other oxidizing agents, for exa'rnple alkali metal .perbor-ates oralkali metal persulfates, :has an :advantageous elfectonthe:metallization. On vegetable fibers, including fibers of regeneratedcellulose, there are obtained by the dyeing and printing methods knownfrom the ice color industry dyestufis which possess in addition to goodgeneral properties of fastness a very good fastness to light.

The production of the dyestufis on vegetable fibers may be carried outat a long goods-to-liquor ratio. Piece goods, warps or bands may be dyedin a continuous manner, or printed by the base or naphtholate printingprocess.

Vegetable fibers, including fibers of regenerated cellulose, may forinstance be impregnated with the alkaline solutions of the couplingcomponents which, in most cases, are not substantive or only littlesubstantive, and freed'f-r'om the excess by squeezing or centrifuging.After an eventual intermediate drying of the impregnated mater-ial, theformation of the dyestuif may be effected as usual in a developing bathcontaining the diazonium'compoundof one of the amines used according tothe process of the present invention,

The new dyestuffs can also be prepared on animal fibers such as wool orsilk, or on synthetic fibers such as pelyamide, acetylcellulose, orpolyvinylalcohol fibers, by the dyeing processes usual for these fiberswhereby valuable dyeing processing good properties of tastness areobtained.

The dyestuffs can also be prepared in substance and converted intocomplex metal compounds by a treatment with agents yielding metal; Themetallization maybe carried out in an aqueous suspension or in anorganic solvent, such, for example, as acetone or dimethylformamide. Thecomplex metal compounds 50 obtained: are suitable for dying" animal andsynthetic fibers, or for coloring organic plastic masses of highmolecular weight.

As coupling components for the process of the present invention theremay be used'comp'ounds coupling in a position vicinal to a hydroxylgroup i.e. aromatic or heterocyclic hydroxy compounds as well ascompounds containing an enolizable orenolized ketomethylenegroup:

Such compounds are,,for example, arylides of aromatic or heterocyclicortho-hyd'roxycarboxylic acids or acylacetic acids, such as arylides.of- 2,3-hydrox-ynaphthoic acid and its derivatives substitutedin6-posi'tionor arylides of Z-hydrOXyanthracene-S carboxylic acid,3-hydroxydiphenylene oxide-Z-carboxylic acid, Z-hydroitycaibazole-S-canboxylic acid, S-hydroxy-LZ,1",2 benzocarbazole-4-carboxylic acid,acetoacetic acid, benzoylacetic acid or terephthaloyl-bis-acetic acid,furthermore the derivatives of phenol substituted in 4'-positi-on, suchas para-cresol, parachlorophenol, 4-hydroxy-1,2-Xylene-,4-hydroxyacetophe none and hydroquinonemonomethylether, the derivativesof a-naphthol substituted in 4-position such as, for ex ample,4-chloro-l-naphthol, 4-methoxy-1-naphthol' and 4- benzoy-l--l-naphtliol,,o-naphthol and its derivatives, such, for example, as6-bromo-2-naphthol, 7-hydroxy-2-rnethoxynaphthalene,1-benzoylamino-7-naphtho1' and 4-phenylazo-1-amino-7-naphthol, as wellas 6-hydroxyquinoline, 2-hydroxycanbazole, 3-hydroxydiphenylene oxideand 1- aryl-3-methyl-5-pyrazolone. In addition to these monohydroxycompounds there can also be used as coupling components polyhydroxycompounds of the aromatic or heterocyclic series coupling inortho-position to the hydroxyl groups, for example resorcinol,benzoylresoncinol; terephthaloylbis resorcinol,2,6--dihydroxynaphthalene and 3,6-dihydroxydiphenylene oxide.

3 As amino compounds which correspond to the above formula and mayadvantageously be used for the process of the present invention, theremay be used compounds wherein the benzene or naphthalene radicals A andB may be substituted by groups which do not impart solubility in watersuch, for example, as halogen atoms, alkyl, alkoxy, trifiuoromethyl,acylarnino, sulfonic acid amide, or carboxylic acid amide groups.

These amino compounds may be prepared in a manner such that2-(2-aminoaryl)-4,5-arylene-1,2,3-triazole-1 oxides corresponding to thegeneral formula wherein A and B represent radicals of the benzene ornaphthalene series, are treated in an alcoholic solution or suspension,at a temperature ranging from about 30 C. to about 150 0., preferablyfrom about 60 C. to about 100 C., and a pressure ranging from about 5 toabout 150 atmospheres gage, preferably from about to about 60atmospheres gage, with hydrogen in the presence of Raney catalysts,such, for example, as Raney nickel.

The following examples serve to illustrate the inven tion but they arenot intended to limit it thereto; the parts being by weight unlessotherwise stated and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter.

EXAMPLE 1 Cotton yarn is treated for 45 minutes at 35 C., at agoods-to-liquor ratio of 1:20, in the following impregation bath,centrifuged, and developed first for 10 minutes at C., and then, afterbeing slowly heated to 90 C. to 95 C., for 20 to minutes at 90 C. to 95C. in the developing bath. The yarn is then rinsed with a solutioncontaining per liter of water 3 cc. of hydrochloric acid of 20 B.,soaped first for 15 minutes at 60 C., then for 15 minutes at 95 C., witha solution containing, per liter of water, 1 gram of a reaction productfrom about 10 mols of ethylene oxide and 1 mol of isododecyl phenol and3 grams of calcined sodium carbonate, rinsed and dried.

Impregnation Bath 3.5 grams of1-(2',3-hydroxynaphtholyamino)-naphthalene are dissolved in 7 cc. ofdenatured ethyl alcohol,

1.75 cc. of sodium hydroxide solution of 38 B.,

3.5 cc. of hot water, and

1.75 cc. of a formaldehyde solution of 30% strength. The solution soobtained is then made up to 1 liter with Water of C.,

3 grams of a condensation product of fatty acids of high molecularweight and protein degradation products, and

10 cc. of sodium hydroxide solution of 38 B.

Developing Bath 3 grams of2-(2'-amino-4'-methoxy-5-acetylaminophenyl)-6-methylbenztriazole in theform of a diazonium compound prepared in the usual manner are dissolvedm 1 liter of water containing 2 grams of a reaction product from about20 mols of ethylene oxide and 1 mol of octadecyl alcohol,

3 cc. of acetic acid of 50% strength,

10 grams of sodium acetate, and

2.5 grams of copper sulfate.

A fast currant dyeing of good properties of fastness is obtained.

When in the above example 2.4 grams of cobaltous chlo- A, ride or 2.8grams of nickel sulfate are used instead of 2.5 grams of copper sulfate,a red-brown dyelng 15 obtained.

EXAMPLE 2 Cotton fabric is padded on the foulard with the followingsolution and dried:

6.4 grams of 2,3-hydroxynaphthoylaminobenzene are dissolved with 15 cc.of sodium hydroxide solution of 38 136.,

20 grams. of Monopole Brilliant Oil and 50 cc. of water of C. and madeup to 1 liter with boiling water.

The dried fabric is developed on the foulard with a solution containing,per liter of water,

10 grams of 2-(2-am,ir1o-4',5-diethoxyphenyl)-6-methoxybenztriazole inthe form of a diazonium compound prepared in the usual manner,

2 grams of a reaction product from about 20 mols of ethylene oxide and 1mol of octadecyl alcohol, and

10 cc. of acetic acid of 50% strength.

After passage of air for 30 seconds, the material is treated for 15seconds at 98 C. with a solution containing per liter of water, 2.5grams of copper sulfate. It is then rinsed hot and cold, soaped with asolution containing, per liter of water, 1 gram of a reaction productfrom about 10 mols of ethylene oxide and 1 mol of isododecyl phenol, and3 grams of calcined sodium carbonate, rinsed and dried.

A bluish brown dyeing of good properties of fastness is obtained.

EXAMPLE 3 Woolen yarn is treated for 45 minutes at 55 C. at agoods-to-liqnor ratio of 1:30 in the following impregnation bath andthen rinsed for 5 minutes at 18 C. to 20 C. with a solution containing,per liter of water, 40 grams of sodium chloride and 3 grams of calcinedsodium carbonate. The material is then allowed to drop off and treatedfirst for 20 to 30 minutes at 18 C. and, after having heated the bath to95 C., for 20 minutes at 95 C. in the developing bath. The yarn is thensoaped for 20 minutes at 40 C. with a solution containing, per liter ofwater, 1 gram of a reaction product from about 20 mols of ethylene oxideand 1 mol of octadecyl alcohol and 1 cc. of ammonia of 25% strength, andthen for 20 minutes at C. with a solution containing, per liter ofwater, 1 gram of a condensation product from an aminoalkyl-sulfonic acidand a fatty acid of high molecular weight, and 0.5 cc. of acetic acid of50% strength, rinsed and dried.

Impregnation Bath 1 gram of 1-(2',3'-hydroxynaphthoylamino)-2-methyl-4-chl'orobenzene and 0.2 gram of sodium hydroxide are dissolved in 4 cc.of denatured ethyl alcohol,

4 cc. of water of 60 C.,

0.5 gram of a condensation product from fatty acids of high molecularweight and protein degradation products and 1 cc. of a formaldehydesolution of 30% strength. The solution so obtained is made up to 1 literwith water of 60 C.,

2.5 grams of a condensation product of fatty acids of high molecularweight and protein degradation products, and

3 grams of sodium carbonate.

Developing Bath 2 grams of 2-(2-aminonaphthyl-1)-benztriazole in theform of a diazonium compound prepared in. the usual manner are dissolvedin 1 liter of water containing 2 grams of a reaction product from about20-rno1s of ethylene oxide and 1 mol of octadecyl alcohol,

2 cc. of acetic acid of 50% strength,

10 grams of sodium acetate, and

1.75 grams of copper sulfate.

A greyish brown dyeing of good properties of fastness' is obtained.When' in the above example 2.1 grams of nickel sulfate are used-insteadof 1.75 grams. of copper sulfate, a yellowish brown dyeing of same goodproperties of fastness is obtained.

EXAMPLE 4 Natural silk is treated for 45 minutes at 25 C. at agoods-to-liquor ratioof -l-:30-in the following impregnation bath,centrifuged, and, while being wet, developed first for 15 minutes at 20C. and then, after slowly heating to 95 C., for 20 minutes at thistemperature in the developing bath. It is then rinsed; acidified with asolution containing, per liter of water, 3 cc. of hydrochloric acid of20 B.', rinsed-againandsoaped for 15 minutes at 95 C. with arsolutioncontaining, per liter of water, 5 gramsof soap, rinsed and-dried.

Impregnation Bath 3 grams of 2,3khydroxynap hthoylaminobenzene are dissolved in 6 cc. of denatured ethyl alcohol,

1.5 cc. of sodium hydroxide solution of 38 B.,

3 cc. of hot water, and

1.5 cc. of a formaldehyde solution of 30% strength.

This solutionismade upto 1 liter with water of 25 C.,

5 grams of a condensation product from fatty acids of high molecularweight and, protein degradation products,

4 cc. of sodium hydroxide solution of 38 B. and 10 grams of sodiumchloride.

Developing Birth 2 grams of 2--( 2--arni-no-4' methoxy-Sbenzolaminophenyl)-6-methoxybenztriazole in the form of a diazoniumcompound prepared. in the usual manner are dissolved in 1 liter of watercontaining 2 grams of a reaction product from about 20 mols of ethyleneoxide and 1 mol of octadecyl alcohol,

3 cc. of-acetic acid of 50% strength,

10 grams of sodium acetate, and

1.75 grams of: copper sulfate.

A garnet dyeing of good properties of fastness is ob tained.

When in the above example 1.65 grams of cobaltous chloride'or 2.1 gramsof nickel sulfate are used instead at 20 C. in a solution containing,per liter of water, 2

grams of sodium nitrite and 3-cc. of hydrochloric acid of 20 B6. Theyarn is allowed to drop-off and then treated in asolution containing,per liter of water, 0.5 cc.

of concentrated ammonia, 2 grams of'sodium acetate, 2.5 grams of coppersulfate and '6 grams of triethanolamine. The bath is. slowly heated from35 C. to 95 C. and maintained for 20 minutes at 95- C. It is then Areddish browndyeingqof goodproperties of fastness is obtained.

When in the above example 24 grams ofzcobaltous chloride and 3flgramsyofaminoacetic acid, ,or 2.8 grams of nickel sulfate and 3 grams ofaminoacetic acid are used instead of 2.5 grams of copper sulfate and 6grams of triethanolamine, a red brown dyeingvis obtained.

EXAMPLE 6" Polyvinyl alcohol yarn is treated for '1 hour at atemperature ranging from. .C...to. .C..at a goodsto-liquor ratio of 1:30in the following solution:

1 gram of 2,3=hydroxynaphthoylaminobenzene. and 0.7 gram of 2'-(2'-amino4' acetylamino 5 methylphenyl)- benztriazole are dissolved with 0.5 cc.of sodiumhydroxide colution of 38 B., '5 cc. of denatured ethyl alcohol,5 cc. of dimethylformamide and 1 cc. of hot water, and the solution isintroducedinto a 'bath containing, per liter of water, 2 grams ofMonopole Brilliant Oil and 5 cc. of sodiumhydroxide solution of 38 Be.

The yarn ist-hen-r-insed and treated for 30: minutes at 65 C. in asolution containing, per liter of water, 2 grams of sodium nitrite and3cc. of-hydrochloric acid of 20 B. The material is allowed to drop offand treated for 15 minutes-at 95 C. with a solutioncontaining, per literof water, 5' grams of sodium acetate, 2 grams of a reaction productf-romabouti-O-molsof ethylene oxide and 1 mol of ,isododecylphenol,v 2.5grams of copper sulfate and 6 grams of triethano-la-rnine. It is thenrinsed and dried.

A brown. red dyeing of good properties offast-ness is obtained.

EXAMPLE-7 12.7 parts 0152- ('2'-amino 4-methoxy-5-methylphenyl)-benztriazole arestirred with 50 partsof water and 40 parts by volume ofhydrochloric acid (density 1.16). After the addition of. ice, the wholeisdiazotizedwith 1.0 parts by volume of a '5 N sodium nitrite solution.The diazo solution-so obtained is combined at 50 -C. witha suspension of15.65 parts of 1- (2,3-hydroxynaphthoylamino)- naphthalene in a solutionof 15 parts of acetic acid, 95.2 parts of sodium acetate and '1' part ofa reaction product from about'20 mols'of ethylene oxide and-l mol ofoleyl alcohol in 1400'parts by volume of water. After completion of thecoupling,- the whole is neutralized with sodium hydroxide solution, anda solution of 12.5 parts of copper sulfate and 45 parts oftriethanolaminein 200 parts by volume of Water is added thereto. Thewhole is then heated -95" C. and treated for 2 hours at; thistemperature. The metalliferous kiyfestuifformed is suction fi red,washed-andd-ried. It-isa'dark powder.

.VEXAMPLE -8- A cottonfabric is padded on-the foulard-with the followingsolution anddrjied: V

14.4 grams of B-naphthol are made into a paste with 30 grams of MonopoleBrilliant Oil and'lt) cc. of sodium hydroxide solution of 38- B;dissolvedandmade up to 1 liter with boiling water containing, per liter,'3' grams of a tragacanth thickening. 7

The dried fabric is developed for 15 to 20' minutes at 20 C. and,afterslowly-heatingto -9-5-' C., for 20--to 30 minutes at 90 C. to 95C..in. the .de'velopiiigliath: described below atalong-goods-to-liquorratio. The-fabric is then rinsed. with asolution..containing, ,p er liter of water, 3 cc. of hydrochloric acidof 20 B., and soaped for 15 minutes at 60 C. witha solution'containing,per liter of water, 2 grams of soap, rinsed and dried;

Developing Bath 1.3 grams of'2-(2' arnino-4 methoxy5'methylphenyl)-benztr-iazole in the form of a-diazonium compound prepared in theusual'manner are dissolved in 1' liter of water containing 2 grams of areaction product from about 20 mols of ethylene oxide and 1 mol ofoctadecyl alcohol;

1 cc. of acetic acid of 50% strength, 7 grams of sodium acetate and 1.25grams of copper sulfate.

A garnet dyeing is obtained.

In the following table are given further components Diazo componentCoupling component Metal Tint2-(2'-m111nO-4',5'-di0th0Xyph8ny1)-6-m0tl1OXybCHZtri-2-(2-3-hydroxynaphthoy1arnino)-naphthalene Copper Garnet.

azole.

Do. 1,(2,3-hydroxynaphthoylarnino)-2,4-dimethoxy-5-chl0roben- Do.

zene. 1-(2,3-hydroxynaphthoylamlno)-2-methyl-4eh1orobenzene Do.1-(2,3-hydroxynaphthoylamin0)-naphthalene urrant. H2 ,3-hydroxynaphthoylamino)-3-nitroben2ene-. l l garnet. 1- (2,3-hydroxynaphthoylamino)-2-methylbenze ne. Currant.1-(2,3-hydroxynaphthoy1amino)-4-chlorobenzene.. Garnet.1-(2,3-hytlr0xynaphthoylarnino)-2-methoxybenzene Bluish garnet.,3-hydroxynaphthoylamine)-3-methoxydipheny1ene oxlde- Garnet.2,3-hydroxynaphthoylaminobenzene ed rown.2-(2,3-hydroxynaphthoylamino)-naphthalene Do.l-(2,3-hydroxynaphthoylamino)-2,4dimeth0xy-5-ehlor0ben Do.

zene. l-(2,3-hydroxynaphthoylamino)-naphthalene D0.1-(2,3-hydroxynaphthoylamino)-3-nitrobenzene D0.1-(2,3-hydroxynaphthoylamino)-2methy1benzene Do.-(2,3-hydroxynaphthoylarnino)4-ehl0robenzene D0. 1-(2 ,3hydroxynaphthoylamino)-2-methoxybenzene Do.2-(2,3'-hydroxynnphthoylamino)-3-meth0xydiphenylene oxide- D0. -lydr0xymphthoylamino)-3-nitrobenzene D-(2.3-hydroxynaphthoylamino)-nnplitha1ene Do.,3-hydrexyuaphthoylamino)4-1nethoxybenzene D0.2-(2,3-hydroxynaphthoylamino)-naphthalene D0.1-g,3'-hydroxynaphthoylamino)-2-meth0xy-4-ehlor0-5-methyl- Do.

enzene. 1-(2,3'-hydroxynaphthoylamino)-2-methoxybenzene D0.1-(2',3-hydroxynaphthoylaraino)-2-methylbcnzene Do.hydroxynaphthoy1amino)-1eh1orobenzene D0,-(2,3-hydroxynaphthoylamtno)-2-rnethyl-4-eh1oroben2ene Do.1-(2,3-hydroxynaphthoylarnino)-2-rnethyl-4methoxybenzene Do. 1-(2,3-hydroxynaphthoylamin0)-2,4dirneth0xy-5-chloroben- Do.

zene. -(2,3-hydrownaphthoylamino)-2,-5.dimeth0xy-4-ehlorobenzene 0.1-(2',3-hydroxynaphthoylamino)-2,5-dimethoxybenzene Do.4,4-bis-(23-l1ydroxynaphthoylarnino)-3,3-dimethoxydi- Do.

phenylene. 1-(2-hydroxyearbazole-3-carb0y1amino)-4-ehl0r0benzene Do.1-(3-l1ydroxydiphenyleneoxide-2-carhoylarnino)-2,5-d1meth- Brown.

oxybenzene V 1-(2,3-hydro:;ynaphthoylarnino)-2ethoxybenzene Red brown.

2-(2,3-hydroxynaphthoylamino)-3-methoxydiphenylene oxide Do. 1-(6-bromo-2,3-hydroxynaphthoylamino)-2-rnethoxyb enzene- Do.1-(5-hydroxy-l,2,1",2-benzoearbazole-4-earb0ylamino)-4- Black blue.

methoxybenzene. D1*(5-hydroxy-1,2,1",2-benzocarbaZole-4-carboy1amino)-2- Currant.

methyl4-methoxybenzene. D1-(2,3-hydroxynaphthoylamino)-2-methyl-5-eh10robenzene Red brown. Do..-1-(2,3-hydroxynaphthoylamino)-2'meth0xy-5ehlorobenzene Do. D1-(2,3-hydroxynaphthoylarnino)-4-methylbenzene Do. Do 1-(2,3-hydro:ynaphthoy1amino)-4-ethoxybenzene D0. D0 l-(3-hydroxydiphenyleneoxide-2-carboylarnino)-naphthalenen, Brown. Dn1-(2,3'-hyclroxynaphthoylamina)-2,4-dirnethylben2ene Red brown. Dn1-(2,3-hydroxynaphthoy1amino)-2,3-dimethy1benzene D0. D0 1-(3-hydroxydiphenylene oxide-2-earboylamino)-2-ethoxyben- Brown.

zene. 2.(zhamino-4-rnethoxy-5-benz0ylaminophenyl)-6-1-(2,3'-hydroxynaphthoylamino)-3-nitrohenzene Garnet.

methoxybenztriazole.

Dn 1-(2',3-hydr0xynaphth0ylamino)-na'ohthalmm Currant. Dn1-(2,3-hydroxynaphthoylamino)-4-methoxybenzene Garnet. D02-(2',3-hydroxynaphthoylamino)naphthalene D0. Dn1-g,3-hydroxynaphthoylamino)-2-methoxy-4ehl0ro-5rnethy1- Do.

enzene. Dn 1-(2,3-hydroxynaphthoylamino)-2-methoxybenzene D0. D01-(2,3-hydroxynaphthoylamino)2-mcthy1benzene-. Currant. Dn1-(2,3-hydroxynaphthoylamin0)-4ehlorobenZene a... Garnet. Dn1-(2,3-hydroxynaphthoylamino)-2-methyl-4-chl0robenzene Currant. Dn1-(2,3'-hydroxynaphthoylamino)-2-methyl-4-methoxybenzene. Do. Dn1-(2',3-hydroxynaphthoy1amino)-2,4-dimethoxy-5-chloroben- Garnet.

zene. Dn 1-(253-hydroxynaphthoy1an1ino)-2,5-dimethoxy-4-ch1oroben- Do.

zene. Dn 1-(2 3-hydroxynaphthoy1amino)-2,5-dimethoxybenzene D0. D0 4,4i1is-(%",3-hydroxynaphthoy1amino)-3,3-dimethoxydi- Currant.

p any D0 1-(2-hydroxycarbazole-3-earboylamino)-4-eh1orobenzene Garnet.Dn 1-(3'-hydroxydiphenylene oxlde-2-earboy1amino)-2,5-dirneth- Brown.

oxybenzene. Dn 1-(2,3-hydroxynaphthoylamlno)-2eth0xybenzene Garnet. Dn2-(2,3-hydroxynaphthoylamino)-3-rneth0xydiphenylene oxide- D0. D01-(6-bromo-2,3-hydroxynaphthoylamino)-2meth0xybenzene Do. Dn1-(5-hydroxy-1,2,1",2"-benzoearbazole-4-carboy1amin0)-4- Greenish black.

methoxybenzene. Dn1-(5-hydroxy-1,2,1",2"-benzocarbazole4-carboylamino)-2-.- do Do.methylt-methoxybenzene. DnTerepgthaloyl-bis-(1-acetylamino-2,4-dimethoxy-5-ch1orobendo Brownyellow.

zene Dn 1-(2,3-hydroxynaphthoy1amino)-2methyl-Emhlorobenzene do Currant.Dn 1, (2 ,3 -hydroxy'naphthoylamin0)-2-methoxy-5 ehlorobenzene- (1 Dnl-(2',3-hydroxynaphthoylamino)4-methylbenzene Dn1-(2',3-hydroxynaphthoylamino)-4-ethoxybenzene Dn1-(3-hydroxydiphenylene oxide-2-carboylamino)-naphthalene.- Dn1-(2',3-hydroxynaphthoylamino)-2,4-dimethy1benzene D1,(2,3-hydroxynaphthoylamino)aedimethylbenzeneu Dn1-(3-hydroxydlpheny1ene oxide-2-carboylarnino)-2-ethoxyben- Dom.2-(2-amine-4-metlioxy-5-methylphenyD-benztrlazolezene. 1-(2-ydroxyanthraeene-3-carboylamino)-2-methy1ben2ene do Grey green.2,3-hydroxynaphthoylaminoben m Red brown.

Diazo component Ooupling component I M t l m2-(2'-amino-4-methoxy-5methylPhenYl)-benztriazolc 1-%, YdrxYn :P l Pi'Redibl'own en ene. Do 1- (2,3'-hydroxynaphthoylamino) 2meth0xybenzene131,-. Do ,1 (2(,3 hydroxynaphthoylamino) Z-meIhylbenZene .13 Do'1-(2,3-hydroxynaphthoylamino) 2 methyl4-ehlorohenzen fob Do1-(2,3-hydroxynophthoylamino)-2-methyl-4-methoxybenzene D' Do1-(2,8-hydroxynaphthoylamino)-2,5-dimethorry-4velnoroben-- D zene. Do1-(2' 3-hydroxynaphthoylamino)-2,5-dimethoxybenzene Do Do 4,43]is-(f",3"-hydr0xynaphthoylamino)-8,3-dimethoxydi- D p eny 1-(3'-hydroxydipheny1ene oxide-2-carboylamino)-2,5-dimeth- D oxybenzene.1-(2',3'-hydroxynaphthoylamino)-2-ethoxybenzene 13 ,2-,(2',3t-hydroxynaphthoylamino)-3-methoxydiphenylene oxide 1) i 1t( bromoZ,3-hydroxynaphthoylamino)-2-methoxybenzene Do.

1-,(5 -hydroxy-1',2,1",2"-benzocarbazole-4-carboylamino)4- 3131 bluemethoxybenzene. E v 1- 'rhydroxy-l',2,1",2-benzocarbazole4earboylamino)=2- "do l. Blueiblack i methyl-4-methoxybenzene.

1t(2',a' hydroxynaphthoylamim)-2methyl-5-chlorobenzene Br 1'- (2,3'hydroxynaphthoylammo)-2-methoxy-5-chlorobenzene J... D1;.(3LhydyoxydiphenyleneoXidB-T-cfllbOYlfiIHlllO) IQ-PhbhfilBIlG- Greybrown 1-(3-hydroxydipheny1ene oxide-2-carboy1emino)-2-ethoxybeu- Brown.zene. (2'. gfi ifii figgzflzi,xy.5'.acety1amlnopheny1)-6 1-(2',shydroxyn p t r .-d0 rant.

me y e 1 z e.

D0 1-(2',3'-hydroxynaphthoylamin0) 2-methyl-4-chlorobenzene d Do2-(2-amine-4'42:ethorgy-W-aoetylammophenyl)-6-ch IOt]))11ztliflz016.

'D 0 2-(2'-amino-4-methoxy-5-methylphenyl)-6-trifiuoro-1-(6-bromo-2,3-hydroxynaphthoylamiuo)-2-methoxyhenzene1,(2,3-hydroxynaphthoylamino)-naphthalene 1,(2',3'-hydroxynaphthoylamino)-2-methy1benzene 1-(2,3-hydroxynaphthoylamino) -2-methyl-4-chlorobenzene1-(6-bromo-2,3-hydroxynaphthoylamino)-2-metho)q benzene 1(2,3!:hydroxynaphthoylamino)-2-methyl 5-ch1oroben zene.1;(2,3-hydroxynaphthoylamino)-2-methyl=4-methoxybenzene 1-(2f,3-hydroxynaphthoylamino)-nephthalene methylbenztriozole.2-ghariiifofi methoxy-5-methylphonyl)-6-methyl- 1-(2,3-hydroxynanhthoylmi o)-1mphthalene enz r azo a.

Do 1-g,3-hydroxynaphthoylamino)-2-methoxy-4-ehloro-5-methy1- .enzene. Do1-(2',3-hydroxynaphthoylamino)-2,4-dimethoxy-5-chlombenzone. D0Terephthaloyl-bis-(1-acetylamine-2,4-dimethoxy-5-ch1 b t zone D02-(2,3-hydroxynaphthoylamino)-3-methoxydiphenylene oxlded Dn1-(2,3'-hydroxynaphthoylaruino) -2-methoxy-fi-chlorobenzene. g3, D1-(2',3'-hydroxynaphthoylamino)-2-methyl-4-chlorobenzene. D0. D01-(6-broruo-2,3-hydroxynaphthoylamino)-2-methoxybenzene Do, D1-(2,3-hydroxynaphthoylamino)-2-methy1-6-chlorobenzene Do,

Tint- Diazocomponent Coupling component Copper-complex Cobalt-complex Nickel-complex 2-(2-amino 4'-methoxy-5'-methylpheny1)- 8-Naphtho1 GarnetRed brown Violet.

benztrlazole.

Do 2chloro-1-naphthol Red brown Red brow 4-ch1oro-l-naphthol. Yellowishred br0w'n Brownish cum-ant.

Resoreinol Yellowish brown Bluish red brown,

3-l1ydroxychphenylene oxide... Yellowish grey brown-.- Greenish greybrown.

Bluish brown Reddish brown.

Yellgw'ish grey brown". o

Grey brown.

3-hydroxydiphenylamine. Brownish violet Yellowish brown.

Z-hydroxycarbazole BllliSh red brown Yellowish dark brown.

2,4dihydroxybenzophenone- Yellowish brown. Bluish grey brown Yellowishred brown.

3-hydroxycarbazo1e Grey brown Bluish red brown Khaki.

p-Chlorophenol ReddiSh grey blue Yellowish grey brown Brownish grey.

EXAMPLE 9 We claim:

297 parts of2-(2'-amino-4'-acetylamino-5'-methylphenyl)-benztriazo1e-1-oxide aresuspended in 3000 parts by volume of methanol and the suspension istreated at 85 C. and a pressure of 60 atmospheres with hydrogen, in thepresence of 30 parts of Raney nickel, in an autoclave provided withstirrer.

The hot solution is freed from the catalyst by suction filtration; oncooling, the 2- (2 amino-4'-acetylamino-5'-methylphenyl) benztriazolecrystallizes in the form of small yellow needles. By concentrating themother liquor, a second fraction is obtained. The product is filteredoff with suction, washed and dried. After recrystallization from ethylalcohol, the

compound melts at a temperature ranging from 220 C.

to 221 C.

The amine obtainable as described in the present example can be coupledaccording to the process of the present invention and the dyestutf soobtained can be treated with agents yielding metal.

1. A water-insoluble complex metal compound containing a metal selectedfrom the group consisting of cobalt, copper, and nickel, of anazo-dyestufi' having the following general formula wherein X representsa member selected from the group from the group consisting of arylamidesof 2,3-hydroxy- 3. The complex copper compound of the azo-dyestuffhaving the formula 12 4. The complex copper compound of the azo-dyestulfhaving the formula NQ-O CH on O-NH-O-mn 5. The complex copper compoundof the azo-dycstuff r having the formula A II N 6. The complex coppercompound of the azo-dyestuff having the formula References Cited in thefile of this patent UNITED STATES PATENTS Laska et a1. Apr. 24, 1928Schindhelm Mar. 1, 1938

1. A WATER-INSOLUBLE COMPLEX METAL COMPOUND CONTAINING A METAL SELECTEDFROM THE GROUP CONSISTING OF COBALT, COPPER, AND NICKEL, OR ANAZO-DYESTUFF HAVING THE FOLLOWING GENERAL FORMULA